Bisoximether derivatives, methods and intermediate products for the production thereof, and their use for combating fungicidal pests and animal pests

ABSTRACT

There are disclosed bisoxime ether derivatives of the formula I                    
     in which the variables have the following meanings: 
     R 1  is halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy; 
     n is 1 to 5, it being possible for the radicals R 1  to be different if n is other than 1; 
     R 2  is C 1 -C 4 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl, it being possible for these groups to be partially or fully halogenated; 
     Q is C(═CHOCH 3 )—COOCH 3 , C(═CHCH 3 )—COOCH 3 , C(═NOCH 3 )—COOCH 3  or C(═NOCH 3 )13 CONHCH 3 ; 
     and salts thereof, processes and intermediates for the preparation of these compounds, and their use for controlling animal pests and harmful fungi.

The present invention relates to bisoxime ether derivatives of theformula I

in which the variables have the following meanings:

R¹ is halogen, C₁-₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy;

n is 1 to 5, it being possible for the radicals R¹ to be different if nis other than 1;

R² is C₁-C₄-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl, it being possible forthese groups to be partially or fully halogenated;

Q is C(═CHOCH₃)—COOCH₃, C(═CHCH₃)—COOCH₃, C(═NOCH₃)—COOCH₃ orC(═NOCH₃)—CONHCH₃;

and to salts thereof.

Moreover, the invention relates to processes and intermediates for thepreparation of these compounds and to their use for controlling animalpests and harmful fungi.

WO-A 95/18789, WO-A 95/21153, WO-A 95/21154 and WO-A 97/05103 disclosebisoxime ether derivatives for controlling harmful fungi and animalpests, but these are not always satisfactory with regard to theiraction.

It is an object of the present invention to provide novel compounds ofthis type with an improved action.

We have found that this object is achieved by the bisoxime etherderivatives I defined at the outset. Moreover, we have found processesand intermediates for their preparation, and also compositionscomprising them for controlling animal pests and harmful fungi and theiruse for this purpose.

The compounds of the formula I differ from the compounds mentioned inthe publications cited above by the design of the bisoxime ether group,which has attached to it a substituted cyclohexyl group.

The compounds I can be obtained by various routes by processes known perse.

When synthesizing the compounds I, it is, in principle, irrelevantwhether it is the group —Q or the group

which is constructed first.

The construction of group —Q is disclosed, for example, in thepublications mentioned at the outset and in those which follow: EP-A 254426, EP-A 370 629, EP-A 463 488, EP-A 472 300 and EP-A 513 580.

When synthesizing the compounds I, a procedure is generally followed inwhich a benzyl derivative of the formula II is reacted with ahydroxyimine of the formula III

In formula II, L¹ is a nucleophilically exchangeable leaving group, forexample halogen or sulfonate groups, preferably chlorine, bromine,iodine, mesylate, tosylate or triflate.

The reaction takes place in an inert organic solvent in the presence ofa base, for example sodium hydride, potassium hydroxide, sodiumhydroxide, sodium methoxide, sodium ethoxide, potassium carbonate ortriethylamine, following the methods described in Houben-Weyl, 4thEdition, Vol. E 14b, p. 370 et seq. and ibid. Vol. 10/1, p. 1189 et seq.

The hydroxyimine III required is obtained, for example, by reacting acorresponding dihydroxyimine IV with the compound of the formula VI

In formula VI, L² is a nucleophilically exchangeable leaving group, forexample halogen or sulfonate groups, preferably chlorine, bromine,iodine, mesylate, tosylate or triflate.

The reaction takes place in an inert organic solvent in the presence ofa base, for example potassium carbonate, potassium hydroxide, sodiumhydride, sodium hydroxide, sodium methoxide, sodium ethoxide, pyridineor triethylamine as described in: Houben-weyl, 4th Edition, Vol. E 14b,p. 307 et seq., p. 370 et seq. and p. 385 et seq.; ibid., 4th Edition,Vol. 10/4, p. 55 et seq., p. 180 et seq. and p. 217 et seq.; ibid., 4thEdition, Vol. E 5, p. 780 et seq.

The compounds of the formula IV can be prepared by known methods [cf.Gazz. Chim. Ital. 59 (1929), p. 719; Collect. Bull. Soc. Chim. Fr. 17(1897), p. 71; C. R. Seances Acad. Sci. Ser. D Vol. 267 (1968), p. 579].

Alternatively, the compounds I may also be obtained by first reactingthe benzyl derivative II with the dihydroxyimino derivative IV to give acorresponding benzyl oxime of the formula V, V subsequently beingreacted with a compound of the formula VI to give I.

The reaction takes place in an inert organic solvent in the presence ofa base, for example potassium carbonate, potassium hydroxide, sodiumhydride, sodium hydroxide, sodium methoxide, sodium ethoxide, pyridineor triethylamine in accordance with the methods described inHouben-Weyl, 4th Edition, Vol. 10/1, p. 1189 et seq., Vol. E 14b, p. 307et seq., p. 370 et seq. and p. 385 et seq., Vol. 10/4, p. 55 et seq., p.180 et seq. and p. 217 et seq., Vol. E 5, p. 780 et seq.

Similarly, it is also possible to prepare the required hydroxyimine ofthe formula III from a carbonylhydroxyimine VII by reacting the latterwith a hydroxylamine IXa or a salt thereof IXb.

In formula IXb, Q^(⊖) is the anion of an acid, in particular of aninorganic acid, for example halide, such as chloride.

The reaction takes place in an inert organic solvent in accordance withthe methods described in EP-A 513 580 and Houben-Weyl, 4th Edition, Vol.10/4, p. 73 et seq., Vol. E 14b, p. 369 et seq. and p. 385 et seq.

The hydroxyimines of the formula VII can be obtained, for example, bythe following synthetic routes [cf. J. Am. Pharm. Assoc. Vol. 35 (1946),p. 15]:

In the reaction scheme above, “Hal” is a halogen atom, in particularchlorine or bromine. The reaction of the compounds VIIa and VIIb, whichfollows a Grignard reaction, is carried out under generally customaryconditions [cf. Organikum (Organic Chemistry), VEB Deutscher Verlag derWissenschaften, 15th Edition, p. 617 et seq., Berlin 1981].

Oxidation of the alcohol VIIc can be effected under generally customaryconditions [cf. Houben-Weyl, Methoden der organischen Chemie (Methods inOrganic Chemistry), Vol. VII/2a, 4th Edition, pp. 699-776, Georg ThiemeVerlag, Stuttgart 1973]. Suitable oxidants are generallyoxygen-transferring compounds such as, for example, hydrogen peroxide,chromium(VI) compounds, manganese compounds, nitrogen-oxygen compounds(for example nitric acid), dimethyl sulfoxide or compounds withpositively induced halogen (for example hypohalites).

Conversion of the ketone VIId into an oxime is normally carried out inan inert organic solvent in the presence of an acid or base [cf.Houben-Weyl, Methoden der organischen Chemie (Methods in OrganicChemistry), Vol. X/4, 4th Edition, pp. 10-27 Georg Thieme Verlag,Stuttgart 1968].

The starting materials VIIa and VIIb are known and some are commerciallyavailable.

Alternatively, the compounds I may also be obtained by first reactingthe benzyl derivative II with the carbonylhydroxyimino derivative VII togive a corresponding benzyloxyimine of the formula VIII, VIIIsubsequently being reacted with the hydroxylamine IXa or a salt thereofIXb to give I.

The reaction is carried out in an inert organic solvent in accordancewith the methods described in Houben-Weyl, Methoden der organischenChemie (Methods in Organic Chemistry), Georg Thieme Verlag Stuttgart1980, 4th Edition, Vol. E 14b, p. 369 et seq., Vol. 10/1, p. 1189 etseq. and Vol. 10/4, p. 73 et seq. or EP-A 513 580.

A further possibility of preparing the compounds I is to react thebenzyl derivative II with N-hydroxyphthalimide and subsequentlysubjecting the product to hydrazinolysis to give the benzylhydroxylamineIIa, which is reacted further with a carbonyl compound X.

The reaction is carried out in an inert organic solvent in accordancewith the methods described in EP-A 463 488 and EP-A 585 751.

The carbonyl compound X is obtained, for example, by reacting acorresponding hydroxyiminocarbonyl compound VIIa with a compound of theformula VI

or by reacting a corresponding dicarbonyl compound XI with ahydroxylamine IXa or a salt thereof IXb

The reactions are carried out in an inert organic solvent in accordancewith the methods described in EP-A 513 580, Houben-Weyl, 4th Edition,Vol. 10/4, p. 55 et seq., p 73 et seq., p. 180 et seq. and p. 217 etseq., Vol. E 14b, p. 307 et seq. and 369 et seq., Vol. E 5, p. 780 etseq.

The compounds of the formula VIIa or XI can be prepared by known methods[cf. J. Chem. Soc. (1955), 3094; Bull. Soc. Chim. Fr. (1969), 2894;Tetrahedron 40 (1984), 2035; J. Org. Chem. USSR (Engl. transl.) Vol. 2(1966) p. 848; J. Org. Chem. Vol. 35 (1970) p. 3007; Tetrahedron Vol. 52(1996) p. 14225; Synth. Commun. Vol. 22 (1992) p. 1049; Synthesis Vol. 6(1986) p. 473; Angew. Chem. Vol. 98 (1986) p. 1134].

Similarly, the compounds I may also be obtained by first reacting thebenzylhydroxylamine IIa with the hydroxyimino derivative VIIa to givethe corresponding benzyloxyimino derivative of the formula V, Vsubsequently being reacted with a compound of the formula VI asdescribed above to give I.

Similarly, the compounds I may also be prepared by first converting thebenzylhydroxylamine IIa with the dicarbonyl derivative of the formula XIinto the benzyloxyimino derivative of the formula VIII and subsequentlyreacting VIII with the hydroxylamine IXa or a salt thereof IXb asdescribed above to give I.

Moreover, the compounds I are also obtained by first converting acompound III with a lactone XII in accordance with the methods describedin EP-A 493 711 to give the corresponding benzoic acid XIII andconverting XIII via the corresponding halides into the cyanocarboxylicacids XIV, which are converted into the α-keto esters XV via a Pinnerreaction (Angew. Chem. 94 (1982), 1) and, if appropriate, reactedfurther to give the a-ketoamides XVI (cf. EP-A 348 766, EP-A 280 185,EP-A 178 826, EP-A 253213, Houben-Weyl, 4th Edition, Vol. E5, p. 941 etseq.).

The α-ketoesters XV and the a-ketoamides XVI can be converted into thecompounds I in accordance with customary processes (cf. EP-A 178 826,EP-A 513 580, EP-A 253 213, EP-A 398 692).

Those compounds I in which Q is C(═NOCH₃)CONHCH₃ may also be obtained byreacting the corresponding esters [Q═C(═NOCH₃)COOCH₃] with methylamine.

Those compounds II which are not already known (EP-A 513 580, EP-A 477631, EP-A 463 488, EP-A 251 082, EP-A 400 417, EP-A 585 751) can beprepared by the methods described therein.

If individual compounds I are not accessible by the routes describedabove, they can be prepared by derivatizing other compounds I.

The reaction mixtures are worked up in the customary manner, for exampleby mixing with water, phase separation and, if appropriate,chromatographic purification of the crude products. In some cases, theintermediates and end products are obtained in the form of colorless orpale brown viscous oils which are purified or freed from volatilecomponents under reduced pressure and at moderately elevatedtemperature. If the intermediates and end products are obtained assolids, they may also be purified by recrystallization or digestion.

Preparation of the compounds I may yield them, owing to their C═C andC═N double bonds, as E/Z isomer mixtures, and these may be separatedinto the individual compounds in the customary manner, for example bycrystallization or chromatography.

If the synthesis yields isomer mixtures, however, separation isgenerally not absolutely necessary since some of the individual isomersmay be converted into each other during processing for use, or upon use(for example with the action of light, acids or bases). Similarconversions may also take place after use, for example in the case ofthe treatment of plants in the treated plant or in the harmful fungi oranimal pest to be controlled. As regards the C═C or C═N double bond ingroup Q, the E isomers of the compounds I are preferred regarding theiractivity (configuration based on the —OCH₃ or the —CH₃ group relative tothe —COOCH₃ or —CONHCH₃ group).

As regards the —C(CH₃)═NOCH₂ double bond, the cis isomers of thecompounds I are preferred regarding their activity (configuration basedon the methyl group relative to the —OCH₂ group).

As regards the C═N—OR² double bond, the cis isomers of the compounds Iare preferred regarding their activity (configuration based on the R²Ogroup relative to the cyclohexyl group).

As regards the variables, the especially preferred embodiments of theintermediates are those of the radicals (R₁)_(n), R² and Q of theformula I.

Collective terms which generally represent the following groups are usedin the definitions of the compounds I given at the outset:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: straight-chain or branched alkyl groups having 1 to 4 carbonatoms such as methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl;

Haloalkyl: straight-chain or branched alkyl groups having 1 to 4 carbonatoms, it being possible for some or all of the hydrogen atoms in thesegroups to be replaced by halogen atoms as mentioned above, for exampleC_(1-C) ₂-haloalkyl such as chloromethyl, dichloromethyl,trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl,1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

Alkoxy: straight-chain or branched alkyl groups having 1 to 4 carbonatoms as mentioned above which are bonded to the skeleton via an oxygenatom (—O—), such as methyloxy, ethyloxy, propyloxy, 1-methylethyloxy,butyloxy, 1-methylpropyloxy, 2-methylpropyloxy or 1,1-dimethylethyloxy;

Haloalkoxy: straight-chain or branched alkyl groups having 1 to 4 carbonatoms, it being possible for some or all of the hydrogen atoms in thesegroups to be replaced by halogen atoms as mentioned above, and thesegroups being bonded to the skeleton via an oxygen atom;

Alkenyl: straight-chain or branched alkenyl groups having 3 to 6 carbonatoms and a double bond wherever desired, such as 1-propenyl,2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl,2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl,1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl,1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;

Alkynyl: straight-chain or branched alkynyl groups having 3 to 6 carbonatoms and a triple bond wherever desired, such as 2-propynyl, 2-butynyl,3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl,1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl,1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl,4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl,1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl,3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl,1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and1-ethyl-1-methyl-2-propynyl;

The term “partially or fully halogenated” is intended to express thatsome or all of the hydrogen atoms in groups characterized thus may bereplaced by identical or different halogen atoms as mentioned above.

Especially preferred with a view to the intended use of the bisoximeether derivatives of the formula I are the following meanings of thesubstituents, in each case alone or in combination:

Particularly preferred compounds I are those in which R¹ is in thetrans-position relative to the linkage of the cyclohexyl ring.

Especially preferred compounds I are those in which R¹ is C_(1-C)₁-alkyl.

Moreover, particularly preferred compounds I are those in which R¹ isC₁-C₄-alkoxy.

Furthermore, preferred compounds I are those in which R¹ is halogen.

Equally, particularly preferred compounds I are those in which the indexn is 1.

Also, particularly preferred compounds I are those in which R² isC₁-C₃-alkyl, C₃-C₄-alkenyl or C₃-C₄-alkynyl.

Other especially preferred compounds I are those in which R² is methylor propargyl.

Moreover, particularly preferred are the compounds I.1

Equally, especially preferred are the compounds I.2.

Especially preferred are the compounds I.3.

Furthermore, especially preferred are the compounds I.4.

Particularly preferred with a view to their use are the compounds Iwhich are compiled in the tables which follow. In these tables, thegroups mentioned for a substituent are also on their own, independentlyof the combination in which they are mentioned, a particularly preferredembodiment of the substituent in question.

Table 1

Compounds of the general formula I.1 in which R² is methyl and (R¹)_(n)for each compound corresponds to one line of Table A

Table 2

Compounds of the general formula I.2, in which R² is methyl and (R¹)_(n)for each compound corresponds to one line of Table A

Table 3

Compounds of the general formula I.3, in which R² is methyl and

(R¹)_(n) for each compound corresponds to one line of Table A

Table 4

Compounds of the general formula I.4, in which R² is methyl and (R¹)_(n)for each compound corresponds to one line of Table A

Table 5

Compounds of the general formula I.1, in which R² is ethyl and (R¹)_(n)for each compound corresponds to one line of Table A

Table 6

Compounds of the general formula I.2, in which R² is ethyl and (R¹)_(n)for each compound corresponds to one line of Table A

Table 7

Compounds of the general formula I.3 in which R² is ethyl and (R¹)_(n)for each compound corresponds to one line of Table A

Table 8

Compounds of the general formula I.4 in which R² is ethyl and (R¹)_(n)for each compound corresponds to one line of Table A

Table 9

Compounds of the general formula I.1 in which R² is n-propyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 10

Compounds of the general formula I.2 in which R² is n-propyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 11

Compounds of the general formula I.3 in which R² is n-propyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 12

Compounds of the general formula I.4 in which R² is n-propyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 13

Compounds of the general formula I.1 in which R² is iso-propyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 14

Compounds of the general formula I.2 in which R² is iso-propyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 15

Compounds of the general formula I.3 in which R² is iso-propyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 16

Compounds of the general formula I.4 in which R² is iso-propyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 17

Compounds of the general formula I.1 in which R² is difluoromethyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 18

Compounds of the general formula I.2 in which R² is difluoromethyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 19

Compounds of the general formula I.3 in which R² is difluoromethyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 20

Compounds of the general formula I.4 in which R² is difluoromethyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 21

Compounds of the general formula I.1 in which R² is2,2,2-trifluoro-1-ethyl and (R¹)_(n) for each compound corresponds toone line of Table A

Table 22

Compounds of the general formula I.2 in which R² is2,2,2-trifluoro-1-ethyl and (R¹)_(n) for each compound corresponds toone line of Table A

Table 23

Compounds of the general formula I.3 in which R² is2,2,2-trifluoro-1-ethyl and (R¹)_(n) for each compound corresponds toone line of Table A

Table 24

Compounds of the general formula I.4 in which R² is2,2,2-trifluoro-1-ethyl and (R¹)_(n) for each compound corresponds toone line of Table A

Table 25

Compounds of the general formula I.1 in which R² is propargyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 26

Compounds of the general formula I.2 in which R² is propargyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 27

Compounds of the general formula I.3 in which R² is propargyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 28

Compounds of the general formula I.4 in which R² is propargyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 29

Compounds of the general formula I.1 in which R² is 3-chloropropargyland (R¹)_(n) for each compound corresponds to one line of Table A

Table 30

Compounds of the general formula I.2 in which R² is 3-chloropropargyland (R¹)_(n) for each compound corresponds to one line of Table A

Table 31

Compounds of the general formula I.3 in which R² is 3-chloropropargyland (R¹)_(n) for each compound corresponds to one line of Table A

Table 32

Compounds of the general formula I.4 in which R² is 3-chloropropargyland (R¹)_(n) for each compound corresponds to one line of Table A

Table 33

Compounds of the general formula I.1 in which R² is allyl and (R¹)_(n)for each compound corresponds to one line of Table A

Table 34

Compounds of the general formula I.2 in which R² is allyl and (R¹)_(n)for each compound corresponds to one line of Table A

Table 35

Compounds of the general formula I.3 in which R² is allyl and (R¹)_(n)for each compound corresponds to one line of Table A

Table 36

Compounds of the general formula I.4 in which R² is allyl and (R¹)_(n)for each compound corresponds to one line of Table A

Table 37

Compounds of the general formula I.1 in which R² is 2-chloroallyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 38

Compounds of the general formula I.2 in which R² is 2-chloroallyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 39

Compounds of the general formula I.3 in which R² is 2-chloroallyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 40

Compounds of the general formula I.4 in which R² is 2-chloroallyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 41

Compounds of the general formula I.1 in which R² is E-3-chloroallyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 42

Compounds of the general formula I.2 in which R² is E-3-chloroallyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 43

Compounds of the general formula I.3 in which R² is E-3-chloroallyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 44

Compounds of the general formula I.4 in which R² is E-3-chloroallyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 45

Compounds of the general formula I.1 in which R² is Z-3-chloroallyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 46

Compounds of the general formula I.2 in which R² is Z-3-chloroallyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 47

Compounds of the general formula I.3 in which R² is Z-3-chloroallyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 48

Compounds of the general formula I.4 in which R² is Z-3-chloroallyl and(R¹)_(n) for each compound corresponds to one line of Table A

Table 49

Compounds of the general formula I.1 in which R² is 3,3-dichloroallyland (R¹)_(n) for each compound corresponds to one line of Table A

Table 50

Compounds of the general formula I.2 in which R² is 3,3-dichloroallyland (R¹)_(n) for each compound corresponds to one line of Table A

Table 51

Compounds of the general formula I.3 in which R² is 3,3-dichloroallyland (R¹)_(n) for each compound corresponds to one line of Table A

Table 52

Compounds of the general formula I.4 in which R² is 3,3-dichloroallyland (R¹)_(n) for each compound corresponds to one line of Table A

TABLE A No. (R¹)_(n) A-1 1-Fluoro A-2 2-Fluoro A-3 3-Fluoro A-4 4-FluoroA-5 1-Chloro A-6 2-Chloro A-7 3-Chloro A-8 4-Chloro A-9 1-Bromo A-1O2-Bromo A-11 3-Bromo A-12 4-Bromo A-13 1-Methyl A-14 2-Methyl A-153-Methyl A-16 4-Methyl A-17 1-Ethyl A-18 2-Ethyl A-19 3-Ethyl A-204-Ethyl A-21 1-n-Propyl A-22 3-n-Propyl A-23 4-n-Propyl A-241-iso-Propyl A-25 3-iso-Propyl A-26 4-iso-Propyl A-27 3-n-Butyl A-284-n-Butyl A-29 3-(2-Butyl) A-30 4-(2-Butyl) A-31 3-(2-Methyl-propyl)A-32 4-(2-Methyl-propyl) A-33 3-tert-Butyl A-34 4-tert-Butyl A-352-Trifluoromethyl A-36 3-Trifluoromethyl A-37 4-Trifluoromethyl A-381-Methoxy A-39 2-Methoxy A-40 3-Methoxy A-41 4-Methoxy A-42 3-EthoxyA-43 4-Ethoxy A-44 3-n-Propoxy A-45 4-n-Propoxy A-46 3-iso-Propoxy A-474-iso-Propoxy A-48 2,4-Dichloro A-49 2-Trifluoromethoxy A-503-Trifluoromethoxy A-51 4-Trifluoromethoxy A-52 1,2-Dichloro A-531,3-Dichloro A-54 1,4-Dichloro A-55 3,4-Dichloro A-56 3,5-Dichloro A-572,4-Difluoro A-58 3,4-Difluoro A-59 3,5-Difluoro A-60 1,2-Dimethyl A-611,3-Dimethyl A-62 1,4-Dimethyl A-63 2,4-Dimethyl A-64 3,4-Dimethyl A-653,5-Dimethyl A-66 3,4-Diethyl A-67 3,5-Diethyl A-68 1-Chloro, 2-MethylA-69 1-Chloro, 3-Methyl A-70 1-Chloro, 4-Methyl A-71 2-Chloro, 4-MethylA-72 3-Chloro, 1-Methyl A-73 3-Chloro, 4-Methyl A-74 3-Chloro, 5-MethylA-75 4-Chloro, 1-Methyl A-76 4-Chloro, 2-Methyl A-77 4-Chloro, 3-Methyl

The compounds I are suitable as fungicides. They are distinguished by anoutstanding activity against a broad spectrum of phytopathogenic fungi,in particular from the classes of the Ascomycetes, Deuteromycetes,Phycomycetes and Basidiomycetes. Some of them act systemically, and theycan be employed in crop protection as foliar- and soil-actingfungicides.

They are especially important for controlling a large number of fungi ona variety of crop plants such as wheat, rye, barley, oats, rice, maize,grass, bananas, cotton, soya, coffee, sugar cane, grapevines, fruitspecies, ornamentals and vegetables such as cucumbers, beans, tomatoes,potatoes and cucurbits, and on the seeds of these plants.

Specifically, they are suitable for controlling the following plantdiseases:

Alternaria species on vegetables and fruit,

Botrytis cinerea (gray mold) on strawberries, vegetables, ornamentalsand grapevines,

Cercospora arachidicola on peanuts,

i Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,

Erysiphe graminis (powdery mildew) on cereals,

Fusarium and Verticillium species on various plants,

Helminthosporium species on cereals,

Mycosphaerella species on bananas and peanuts,

Phytophthora infestans on potatoes and tomatoes,

Plasmopara viticola on grapevines,

Podosphaera leucotricha on apples,

Pseudocercosporella herpotrichoides on wheat and barley,

Pseudocercosporella species on hops and cucumbers,

Puccinia species on cereals,

Pyricularia oryzae on rice,

Rhizoctonia species on cotton, rice and turf,

Septoria nodorum on wheat,

Uncinula necator on grapevines,

Ustilago species on cereals and sugar cane, and

Venturia species (scab) on apples and pears.

Moreover, the compounds I are suitable for controlling harmful fungisuch as Paecilomyces variotii in the protection of materials (eg. wood,paper, paint dispersions, fibers and fabrics) and in the protection ofstored products.

The compounds I are applied by treating the fungi, or the plants, seeds,materials or the soil to be protected against fungal infection, with afungicidally active amount of the active ingredients. Application can beeffected both before and after infection of the materials, plants orseeds by the fungi.

In general, the fungicidal compositions comprise from 0.1 to 95,preferably 0.5 to 90% by weight of active ingredient.

When used in crop protection, the rates of application are from 0.01 to2.0 kg of active ingredient per ha, depending on the nature of theeffect desired.

In the treatment of seed, amounts of active ingredient of from 0.001 to0.1 g, preferably 0.01 to 0.05 g, are generally required per kilogram ofseed.

When used in the protection of materials or stored products, the rate ofapplication of active ingredient depends on the nature of the field ofapplication and on the effect desired. Rates of applicationconventionally used in the protection of materials are, for example,from 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredientper cubic meter of material treated.

Moreover, the compounds of the formula I are suitable for efficientlycontrolling animal pests from the classes of the insects, arachnids andnematodes. They can be employed in crop protection and in the hygiene,stored-product and veterinary sector for controlling animal pests. Inparticular, they are suitable for controlling the following animalpests:

insects from the order of the lepidopterans (Lepidoptera), for exampleAgrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsiagemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius,Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneurafumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydiapomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella,Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella,Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholithafunebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens,Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea,Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria,Laphygma exigua, Leucoptera coffeella, Leucoptera scitella,Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis,Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosomaneustria, Mamestra brassicae, orgyia pseudotsugata, Ostrinia nubilalis,Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalerabucephala, Phthorimaea operculella, Phyllocnistis citrella, Pierisbrassicae, Plathypena scabra, Plutella xylostella, Pseudoplusiaincludens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotrogacerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodopteralittoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrixviridana, Trichoplusia ni and Zeiraphera canadensis,

beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus,Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar,Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophaguspiniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum,Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotomatrifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnematibialis, Conoderus vespertinus, Crioceris asparagi, Diabroticalongicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachnavarivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobiusabietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lemabilineata, Lema melanopus, Leptinotarsa decemlineata, Limoniuscalifornicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethesaeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae,Ortiorrhynchus [sic] sulcatus, Otiorrhynchus ovatus, Phaedoncochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phylloperthahorticola, Phyllotreta nemorum, Phyllotreta striolata, Popilliajaponica, Sitona lineatus and Sitophilus granaria,

dipterans (Diptera), for example Aedes aegypti, Aedes vexans, Anastrephaludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana,Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola,Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae,Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis,Glossina morsitans, Haematobia irritans, Haplodiplosis equestris,Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyzatrifolii, Lucilia caprina [sic], Lucilia cuprina, Lucilia sericata,Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscinastabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbiaantiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi,Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea and Tipulapaludosa,

thrips (Thysanoptera), eg. Frankliniella fusca, Frankliniellaoccidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae,Thrips palmi and Thrips tabaci,

hymenopterans (Hymenoptera), eg. Athalia rosae, Atta cephalotes, Attasexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea,Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,

heteropterans (Heteroptera), eg. Acrosternum hilare, Blissusleucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercusintermedius, Eurygaster integriceps, Euschistus impictiventris,Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezaraviridula, Piesma quadrata, Solubea insularis and Thyanta perditor,

homopterans (Homoptera), eg. Acyrthosiphon onobrychis, Adelges laricis,Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycauduscardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusianordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthumpseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiphumeuphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum,Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius,Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri,Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphis mala,Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa,Trialeurodes vaporariorum and Viteus vitifolii,

termites (Isoptera), eg. Calotermes flavicollis, Leucotermes flavipes,Reticulitermes lucifugus and Termes natalensis,

orthopterans (Orthoptera), eg. Acheta domestica, Blatta orientalis,Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa,Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum,Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus,Nomadacris septemfasciata, Periplaneta americana, Schistocercaamericana, Schistocerca peregrina, Stauronotus maroccanus and Tachycinesasynamorus,

Arachnoidea, such as arachnids (Acarina), eg. Amblyomma americanum,Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilusdecoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobiapraetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyessheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus,Ornithodorus moubata, Otobius megnini, Paratetranychus pilosus,Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemuslatus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalusevertsi, Sarcoptes scabiei, Tetranychus cinnabarinus, Tetranychuskanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychusurticae,

nematodes such as root knot nematodes, eg. Meloidogyne hapla,Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, eg.Globodera rostochiensis, Heterodera avenae, Heterodera glycines,Heterodera schachtii, Heterodera trifolii, stem eelworms and foliarnematodes, eg. Belonolaimus longicaudatus, Ditylenchus destructor,Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidoruselongatus, Radopholus similis, Rotylenchus robustus, Trichodorusprimitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius,Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatusand Pratylenchus goodeyi.

The rate of application of active ingredient for controlling animalpests is from 0.1 to 2.0, preferably 0.2 to 1.0, kg/ha under fieldconditions.

The compounds I can be converted into the customary formulations, eg.solutions, emulsions, suspensions, dusts, powders, pastes and granules.The use form depends on the particular purpose; it is intended to ensurein each case a fine and uniform distribution of the compound accordingto the invention.

The formulations are prepared in a known manner, eg. by extending theactive ingredient with solvents and/or carriers, if desired usingemulsifiers and dispersants, it also being possible to use other organicsolvents as auxiliary solvents if water is used as the diluent.Auxiliaries which are suitable are essentially: solvents such asaromatics (eg. xylene), chlorinated aromatics (eg. chlorobenzenes),paraffins (eg. mineral oil fractions), alcohols (eg. methanol, butanol),ketones (eg. cyclohexanone), amines (eg. ethanolamine,dimethylformamide) and water; carriers such as ground natural minerals(eg. kaolins, clays, talc, chalk) and ground synthetic minerals (eg.highly disperse silica, silicates); emulsifiers such as nonionic andanionic emulsifiers (eg. polyoxyethylene fatty alcohol ethers,alkylsulfonates and arylsulfonates) and dispersants such aslignin-sulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids andtheir alkali metal and alkaline earth metal salts, salts of sulfatedfatty alcohol glycol ether, condensates of sulfonated naphthalene andnaphthalene derivatives with formaldehyde, condensates of naphthalene orof napthalenesulfonic acid with phenol or formaldehyde, polyoxyethyleneoctylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether,alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite wasteliquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, eg. benzene, toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, chloroform, carbontetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone,strongly polar solvents, eg. dimethylformamide, dimethyl sulfoxide,N-methylpyrrolidone and water.

Powders, materials for spreading and dusts can be prepared by mixing orconcomitantly grinding the active substances with a solid carrier.

Granules, eg. coated granules, impregnated granules and homogeneousgranules, can be prepared by binding the active ingredients to solidcarriers. Examples of solid carriers are mineral earths, such as silicagel, silicas, silica gels [sic], silicates, talc, kaolin, attaclay,limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth,calcium sulfate, magnesium sulfate, magnesium oxide, ground syntheticmaterials, fertilizers, eg. ammonium sulfate, ammonium phosphate,ammonium nitrate, ureas, and products of vegetable origin, such ascereal meal, tree bark meal, wood meal and nutshell meal, cellulosepowders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active ingredient. Theactive ingredients are employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum).

The following are examples of formulations:

I. 5 parts by weight of a compound according to the invention are mixedintimately with 95 parts by weight of finely divided kaolin. This givesa dust which comprises 5% by weight of the active ingredient.

II. 30 parts by weight of a compound according to the invention aremixed intimately with a mixture of 92 parts by weight of pulverulentsilica gel and 8 parts by weight of paraffin oil which had been sprayedonto the surface of this silica gel. This gives a formulation of theactive ingredient with good adhesion properties (comprises 23% by weightof active ingredient).

III. 10 parts by weight of a compound according to the invention aredissolved in a mixture composed of 90 parts by weight of xylene, 6 partsby weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol ofoleic acid N-monoethanolamide, 2 parts by weight of calciumdodecylbenzenesulfonate and 2 parts by weight of the adduct of 40 mol ofethylene oxide and 1 mol of castor oil (comprises 9% by weight of activeingredient).

IV. 20 parts by weight of a compound according to the invention aredissolved in a mixture composed of 60 parts by weight of cyclohexanone,30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7mol of ethylene oxide and 1 mol of isooctylphenol and 5 parts by weightof the adduct of 40 mol of ethylene oxide and 1 mol of castor oil(comprises 16% by weight of active ingredient).

V. 80 parts by weight of a compound according to the invention are mixedthoroughly with 3 parts by weight of sodiumdiisobutylnaphthalene-alpha-sulfonate, 10 parts by weight of the sodiumsalt of a lignosulfonic acid from a sulfite waste liquor and 7 parts byweight of pulverulent silica gel, and the mixture is ground in a hammermill (comprises 80% by weight of active ingredient)

VI. 90 parts by weight of a compound according to the invention aremixed with 10 parts by weight of N-methyl-α-pyrrolidone, which gives asolution which is suitable for use in the form of microdrops (comprises90% by weight of active ingredient).

VII. 20 parts by weight of a compound according to the invention aredissolved in a mixture composed of 40 parts by weight of cyclohexanone,30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weightof the adduct of 40 mol of ethylene oxide and 1 mol of castor oil.Pouring the solution into 100,000 parts by weight of water and finelydistributing it therein gives an aqueous dispersion which comprises0.02% by weight of the active ingredient.

VIII. 20 parts by weight of a compound according to the invention aremixed thoroughly with 3 parts by weight of sodiumdiisobutylnaphthalene-α-sulfonate, 17 parts by weight of the sodium saltof a lignosulfonic acid from a sulfite waste liquor and 60 parts byweight of pulverulent silica gel, and the mixture is ground in a hammermill. Finely distributing the mixture in 20,000 parts by weight of watergives a spray mixture which comprises 0.1% by weight of the activeingredient.

The active ingredients can be used as such, in the form of theirformulations or the use forms prepared therefrom, eg. in the form ofdirectly sprayable solutions, powders, suspensions or dispersions,emulsions, oil dispersions, pastes, dusts, materials for spreading, orgranules, by means of spraying, atomizing, dusting, spreading orpouring. The use forms depend entirely on the intended purposes; it isintended to ensure in each case the finest possible distribution of theactive ingredients according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances, as suchor dissolved in an oil or solvent, can be homogenized in water by meansof wetter, tackifier, dispersant or emulsifier. Alternatively, it ispossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,and such concentrates are suitable for dilution with water.

The active ingredient concentrations in the ready-to-use products can bevaried within relatively wide ranges. In general, they are from 0.0001to 10%, preferably from 0.01 to 1%.

The active ingredients may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active ingredient, or even to apply theactive ingredient without additives.

Various types of oils, herbicides, fungicides, other pesticides, orbactericides may be added to the active ingredients, if appropriate justimmediately prior to use (tank mix). These agents can be admixed withthe compositions according to the invention in a weight ratio of 1:10 to10:1.

In the use form as fungicides, the compositions according to theinvention can also be present together with other active ingredients,eg. with herbicides, insecticides, growth regulators, fungicides or elsewith fertilizers. Mixing the compounds I or the compositions comprisingthem in the use form as fungicides with other fungicides frequentlyresults in a broader fungicidal spectrum of action.

The following list of fungicides together with which the compoundsaccording to the invention can be used is intended to illustrate thepossible combinations, but not to impose any limitation:

sulfur, dithiocarbamates and their derivatives, such as iron(III)dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate,manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuramdisulfides [sic], ammonia complex of zinc(N,N-ethylenebisdithiocarbamate), ammonia complex of zinc(N,N′-propylenebisdithiocarbamate), zinc(N,N′-propylenebisdithiocarbamate),N,N′-polypropylenebis(thiocarbamoyl)disulfide;

nitro derivatives, such as dinitro(1-methylheptyl)phenyl crotonate,2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl5-nitro-isophthalate;

heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate,2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethylphthalimidophosphonothioate,5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole,2,3-dicyano-1,4-dithioanthraquinone,2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl1-(butylcarbamoyl)-2-benzimidazolecarbamate,2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole,2-(4-thiazolyl)benzimidazole,N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide,N-trichloromethylthiotetrahydrophthalimide,N-trichloromethylthiophthalimide;

N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfodiamide,5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene,4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine-2-thiol1-oxide, 8-hydroxyquinoline or its copper salt,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide,2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide,2,4,5-trimethylfuran-3-carboxanilide,2,5-dimethylfuran-3-carboxcyclohexylamide,N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide,2-methylbenzanilide, 2-iodobenzanilide,N-formyl-N-morpholine-2,2,2-trichloroethyl acetal,piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide,1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,2,6-dimethyl-N-tridecylmorpholine or its salts,2,6-dimethyl-N-cyclododecylmorpholine or its salts,N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,N-[3-(p-tert-butylphenyl)-2-methylpropyl]piperidine,1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolylurea,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,(2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole,α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,bis(p-chlorophenyl)-3-pyridinemethanol,1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene,1,2-bis(3-methoxycarbonyl-2-thioureido)benzene;

strobilurins such as methylE-methoxyimino-[α-(o-tolyloxy)-o-tolyl]acetate, methylE-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate,N-methyl-E-methoxy-imino-[α-(2-phenoxyphenyl)]acetamide,N-methyl-E-methoxyimino-[α-(2,5-dimethylphenoxy)-o-tolyl]acetamide;

anilinopyrimidines such as N-(4,6-dimethylpyrimidin-2-yl)aniline,N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline,N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline;

phenylpyrroles such as4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile;

cinnamamides such as3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloylmorpholide;

and a variety of fungicides such as dodecylguanidine acetate,3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide,hexachlorobenzene, methylN-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate,DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)alanine methyl ester,N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-amino butyrolactone,DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl) alanine methyl ester,5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,3-(3,5-dichlorophenyl)-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin,N-(3,5-dichlorophenyl)-1,2-methylcyclopropane-1,2-dicarboximide,2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide,1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole,2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol,N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,1-((bis(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole.

SYNTHESIS EXAMPLES

With due modification of the starting compounds, the protocols shown inthe synthesis examples below were used for obtaining further compoundsI. The resulting compounds, together with physical data, are listed inthe Tables which follow.

Example 1 Preparation of 1-(4-methylcyclohexyl)propan-1-ol

180 ml (0.36 mol) of a 2 M ethylmagnesium chloride solution intetrahydrofuran (THF) was first treated with a solution of 37.8 g (0.3mol) of 4-methylcyclohexanecarbaldehyde (cis/trans) in 70 ml of THF andthen stirred under protective gas atmosphere for approximately 16 hoursat 20-25° C. After addition of 250 ml of 15% by weight ammonium chloridesolution, the mixture was acidified with semiconcentrated hydrochloricacid and then extracted with methyl tert-butyl ether (MTBE). Washing ofthe combined organic phases with water and drying gave 44 g of1-(4-methylcyclohexyl)propan-1-ol as a colorless oil. According to ¹HNMR analysis, the ratio between the cis and trans isomers in the mixtureamounted to approximately 35:65.

IR (film): 3371, 2946, 2921, 2867, 1455, 1448, 1376, 1067, 1043, 946cm⁻¹.

Example 2 Preparation of 4-methylcyclohexyl ethyl ketone

A solution of 44 g (0.3 mol) of the alcohol of Example 1 in 200 ml ofmethyl tert-butyl ether (MTBE) was treated at not more than 20° C. witha solution of 42.9 g of Na₂Cr₂O₇*2H₂O in 210 ml of water and 35 ml ofconcentrated H₂SO₄. After the mixture had been stirred for approximately16 hours at 20-25° C., the phases were separated and the aqueous phasewas extracted with MTBE. After washing with water and drying, thecombined organic phases [lacuna] distilled. The distillation gave 34.3 gof 4-methylcyclohexyl ethyl ketone as a colorless oil of b.p.₅₀ of114-116° C. According to ¹³C NMR analysis, the ratio between the cis andtrans isomers in the mixture amounted to approximately 30:70.

IR (film): 2926, 2868, 1709, 1457, 1413, 1377, 1348, 1148, 1109, 952cm⁻¹.

Example 3 Preparation of (E)-1-(4-methylcyclohexyl)-1-oxopropane 2-oxime

A solution of 34 g (0.22 mol) of the ketone of Example 2 in 195 ml oftoluene was treated at −20° C. with 73 ml of saturated etheric HClsolution and then with a solution of 26 g (0.25 mol) of n-butyl nitritein 65 ml of diethyl ether. After the reaction mixture had been stirredfor two hours at 0° C. and for approx. 16 hours at 20-25° C., it waspoured into ice-water and extracted with methyl tert-butyl ether (MTBE).The organic phase was extracted with a 5% strength sodium hydroxidesolution, and the alkaline aqueous phase was acidifed with dilutehydrochloric acid and then extracted with MTBE. The organic phase waswashed and dried. Removal of the solvent by distillation andrecrystallization from n-hexane gave 19.2 g of the title compound asbeige crystals. According to ¹H NMR analysis, the compound was presentas the trans isomer.

IR (KBr): 3320, 2951, 2945, 2935, 2919, 1663, 1449, 1368, 1008 cm⁻¹.

Example 4 Preparation of(E,E)-1-(4-methylcyclohexyl)-2-hydroxyimino-1-propane O-methyloxime

A mixture of 18.3 g (0.1 mol) of the oxime of Example 3, 24 g ofpyridine and 12.5 g (0.15 mol) of O-methylhydroxylamine hydrochloride in200 ml of methanol was first stirred for approx. 16 hours at 20-25° C.and then poured into ice-water, acidified with dilute hydrochloric acidand extracted with methyl tert-butyl ether (MTBE). The organic phase waswashed with water, dried and then freed from solvent. The solution ofthe residue in 300 ml of toluene was treated with 4.1 g of AlCl₃ andstirred for 8 hours at 60° C. and then for a further 16 hours at 20-25°C. The solvent was distilled off and the residue was taken up inmethylene chloride. The organic phase was washed with 5% strengthhydrochloric acid and water, dried and then freed from solvent. Aftersilica gel chromatography (cyclohexane/MTBE 20:1), 9.7 g of the titlecompound were obtained as an ochre oil. According to ¹H NMR analysis,the compound was present as the trans isomer.

IR (film): 2948, 2926, 2868, 2845, 1451, 1057, 1006, 976, 909, 865 cm⁻¹.

Example 5 Preparation of I-1

A solution of 2.12 g (10 mmol) of the bisoxime of Example 4 and 2.86 g(10 mmol) of methyl 2-bromomethylphenylglyoxylate trans-o-methyloxime[EP-A 254 426] in 30 ml of N,N-dimethylformamide (DMF) was treated with1.98 g of 30% strength methanolic sodium methoxide solution and stirredfor approx. 16 hours at 20-25° C. The mixture was poured into ice-waterand then extracted with methyl tert-butyl ether (MTBE). The organicphase was washed with water and dried and then freed from solvent. Afterchromatography on silica gel (cyclohexane/MTBE 10:1), 3.44 g of thetitle compound were obtained as colorless crystals. According to ¹H NMRanalysis, the compound was present as the trans isomer.

Example 6 Preparation of I-2

A solution of 2.3 g (5.5 mmol) of compound I-1 of Example 5 in 30 ml oftetrahydrofuran (THF) was treated with 4.3 g of 40% strength aqueousmethylamine solution and stirred for three hours at 45° C. and forapprox. 16 hours at 20-25° C. After the solvent had been distilled off,the residue was taken up in methyl tert-butyl ether (MTBE), and thesolution was washed with water and dried. After the solvent had beendistilled off, 2.1 g of the title compound were obtained as colorlesscrystals. According to ¹H NMR analysis, the compound was present as thetrans isomer.

TABLE I Physical data [m.p.: ° C.; No. Formula (R¹⁾ _(n) R² IR: cm⁻¹¹H-NMR: ppm] I-1 I.1 4-methyl methyl 67-69; 1736, 1220, 1077, 1058,1021, 1009, 992, 905, 865, 778 I-2 I.2 4-methyl methyl 107-109; 3370,1659, 1530, 1059, 1051, 1043, 1014, 996, 906, 755 I-3 I.3 4-methylmethyl 2947, 2926, 1711, 1635, 1256, 1130, 1111, 1055, 1013, 908 I-4 I.44-methyl methyl 2948, 2929, 2868, 1719, 1450, 1435, 1252, 1049, 1013,907 I-5 I.4 4-methyl propargyl 1718, 1450, 1435, 1252, 1207, 1038 I-6I.3 4-methyl propargyl 1710, 1634, 1255, 1129, 1111, 1043 I-7 I.34-methoxy methyl 1711, 1635, 1256, 1130, 1103, 1056 I-8 I.4 4-methoxymethyl 1719, 1253, 1102, 1051, 1006 I-9 I.1 4-methoxy methyl 1737, 1305,1101, 1071, 1043, 1013 I-10 I.2 4-methoxy methyl 1660, 1530, 1105, 1097,1060, 1043 I-11 I.1 2-methyl methyl 1730, 1219, 1070, 1020, 958, 886I-12 I.4 2-methyl methyl 5.0(2H); 3.85(3H); 3.7(3H); 2.0(3H) I-13 I.32-methyl methyl 1712, 1636, 1256, 1129, 1055 I-14 I.2 2-methyl methyl1742, 1052, 957, 686

Examples for the Action Against Harmful Fungi

The fungicidal action of compounds of the general formula I wasdemonstrated by the following experiments:

The active ingredients, separately or together, were formulated as a 10%emulsion in a mixture of 70% by weight of cyclohexane, 20% by weight ofNekanil® LN (Lutensol® AP6, wetter having emulsifying and dispersantaction, based on ethoxylated alkylphenols) and 10% by weight of Wettol®EM (non-ionic emulsifier based on ethoxylated castor oil) and dilutedwith water to give the desired concentration.

Compounds A, B, C and D, which are known from WO-A 97/05103 as NumbersA.2 of Tables No. 41, 42, 43 and 44, acted as comparison activeingredients:

No. Disclosed in WO-A 97/05103 R² Q A Tab. 41, No. A.2 methylC(═CHOCH₃)COOCH₃ B Tab. 42, No. A.2 methyl C(═CHCH₃)COOCH₃ C Tab. 43,No. A.2 methyl C(═NOCH₃)COOCH₃ D Tab. 44, No. A.2 methylC(═NOCH₃)CONHCH₃

Example 1 Activity Against Botrytis cinerea on capsicum leaves

Capsicum seedlings cv. “Neusiedler Ideal Elite” were allowed to fullydevelop 4 to 5 leaves and then sprayed to runoff point with an aqueouspreparation of active ingredient which had been made up from a stocksolution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier.Next day, the treated plants were inoculated with a spore suspension ofBotrytis cinerea which contained 1.7×10⁶ spores/ml in a 2% strengthaqueous Biomalz solution. The test plants were subsequently placed intoa controlled-environment cabinet at 22 to 24° C. and high atmospherichumidity. After 5 days, the extent of fungal infection on the leaves wasdetermined visually in %.

In this test, the plants which had been treated with 250 ppm of activeingredients I-1, I-2, I-3 or I-4 showed a disease level of 0 to 25%,while the plants which had been treated with 250 ppm of the comparisonactive ingredients A, B, C and D, respectively, showed a disease levelof 60 to 90% and the untreated plants also of 90%.

Example 2 Curative Activity Against Puccinia recondita on Wheat (LeafRust on Wheat)

Leaves of wheat seedling cv. “Kanzler” grown in pots were dusted withleaf rust spores (Puccinia recondita). The pots were then placed for 24hours into a chamber with high atmospheric humidity (90 to 95%) and 20to 22° C. During this time, the spores germinated and the germ tubespenetrated the leaf tissue. Next day, the infected plants were sprayedto runoff with an aqueous active ingredient preparation made with astock solution consisting of 10% of active ingredient, 63% ofcyclohexanone and 27% of emulsifier. After the spray coating had driedon, the test plants were grown in the greenhouse for 7 days attemperatures between 20 and 22° C. and a relative atmospheric humidityof 65 to 70%. The extent of rust development on the leaves was thendetermined.

In this experiment, a maximum disease level of 5% was shown by theplants treated with 1 ppm of the active ingredients I-2, I-3, I-7 andI-10, while the disease level of the untreated plants and of those whichhad been treated with 1 ppm of the comparative active ingredients A or Dwas 90%.

Example 3 Activity Against Plasmopara viticola

Leaves of grapes cv. “Müller-Thurgaul” in pots were sprayed to runoffwith aqueous active ingredient preparations made with a stock solutionof 10% active ingredient, 63% cyclohexanone and 27% of emulsifier. Inorder to be able to assess the long-term action of the substances, thespray coating was allowed to dry off and the plants were then placed inthe greenhouse for 7 days. Only then were the leaves inoculated with anaqueous zoospore suspension of Plasmopara viticola. Then, the vines werefirst placed for 48 hours into a water-vapor-saturated chamber at 24° C.and then for 5 days in the greenhouse at temperatures between 20 and 30°C. After this time, the plants were returned to a humid chamber for 16hours to accelerate sporangiophore eruption for 16 hours. The extent ofthe disease development on the undersides of the leaves was thendetermined visually.

In this experiment, a maximum disease level of 3% was shown by theplants which had been treated with 16 ppm of the active ingredients I-2and I-10, while the disease level of the plants which had been treatedwith 16 ppm of the comparative active ingredient D was 60% and of theuntreated plants 85%.

Examples for the Action Against Animal Pests

The action of the compounds of the formula I against animal pests wasdemonstrated by the following experiments:

The active ingredients were formulated

a. as a 0.1% strength solution in acetone or

b. as a 10% emulsion in a mixture of 70% by weight of cyclohexanone, 20%by weight of Nekanil® LN (Lutensol® AP6, wetter having emulsifying anddispersant action, based on ethoxylated alkylphenols) and 10% by weightof Wettol® EM (non-ionic emulsifier based on ethoxylated castor oil)

and diluted to give the desired concentration, using acetone in the caseof a. and water in the case of b.

After the tests had been concluded, the lowest concentration wasdetermined for each case at which the compounds still showed aninhibition or mortality of 80 to 100% in comparison to untreated control(limit or minimal concentration).

In these experiments too, compounds A, B, C and D, which are known fromWO-A 97/05103 as Numbers A.2 of Tables No. 41, 42, 43 and 44, acted ascomparison active ingredients.

Example 1 Action Against Aphis fabae (Black Louse [sic]), Contact Action

Severely infested dwarf beans (Vicia faba) in the four-leaf stage weretreated with aqueous formulations of active ingredient. The mortalityrate was determined after 24 hours.

In this experiment, the active ingredients I-1 and I-4 showed limitconcentrations of 80 to 100 ppm, while the comparison active ingredientsA and C showed limit concentrations of 100 ppm.

Example 2 Action Against Prodenia litura (Egyptian Cotton Leafworm),Contact and Stomach Action

Filter disks (Ø 9 cm) which had been treated with aqueous formulationsof active ingredient were populated with five caterpillars. Two maizeleaf sections which had been immersed in a solution of active ingredientwere also introduced. The first assessment was carried out after fourhours. In the event that at least one caterpillar was still alive, afeed mix was added. The mortality was determined after 24 hours.

In this experiment, the active ingredients I-1 to I-7 and I-10, I-3[sic] showed limit concentrations of 0.04 to 0.2 ppm, while thecomparison active ingredients A, B and C showed limit concentrations ofover 0.2 ppm.

Example 3 Action Against Nephotettix cincticeps (Green Rice Leafhopper),Contact Action

Filter disks (Ø 9 cm) were treated with 1 ml of aqueous formulations ofthe active ingredient and subsequently populated with five adultleafhoppers. The mortality was determined after 24 hours.

In this experiment, the active ingredients I-3 and I-4 showed limitconcentrations of 0.04 mg, while the comparison active ingredients A andB showed limit concentrations of 0.2 mg.

Example 4 Action Against Nephotettix cincticeps (Crop Spray Experiment)

Rice plants grown in pots (plant height approximately 8 cm) were sprayedto runoff point with aqueous formulations of active ingredients. Afterdrying, the plants were populated with 20 adult leafhoppers. Themortality was determined after 24 hours.

In this experiment, the active ingredients I-3 and I-4 showed limitconcentrations of 20 to 40 ppm, while the comparison active ingredientsA and B showed limit concentrations of 400 ppm.

Example 5 Action Against Tetranychus telarius*) (Red Spider Mite)

*) syn. urticae

Dwarf beans in pots which had developed the second true leaf pair weresprayed to runoff point with aqueous preparations of active ingredients.The plants were severely infested with adult mites and eggs. After 5days in the greenhouse, the infestation level was determined by means ofa stereomicroscope.

In this experiment, the active ingredients I-1 and I-3 to I-6 showedlimit concentrations of 20 to 40 ppm, while the comparison activeingredients A, B and C showed limit concentrations of 100 ppm or more.

We claim:
 1. A bisoxime ether compound of formula I

wherein R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy; n is 1 to 5, and the radicals R¹ are identical ordifferent when n is other than 1; R² is C₁-C₄-alkyl, C₃-C₆-alkenyl orC₃-C₆-alkynyl, and these groups are unsubstituted, partially halogenatedor fully halogenated; Q is C(═CHOCH₃)—COOCH₃, C(═CHCH₃)—COOCH₃,C(═NOCH₃)—COOCH₃ or C(═NOCH₃)—CONHCH₃; or a salt thereof.
 2. A processfor the preparation of the compound of formula I defined in claim 1,which comprises reacting a benzyl compound of formula II

wherein L¹ represents a nucleophilically exchangeable leaving group,with a hydroxyimine of formula III


3. A process for the preparation of the compound of formula I defined inclaim 1, which comprises reacting a benzyl compound of formula II

wherein L¹ represents a nucleophilically exchangeable leaving group,with a dihydroxyimine of formula IV

to give a compound of formula V

and subsequently reacting V with a compound of formula VI R²—L²  (VI)wherein L² is a nucleophilically exchangeable leaving group, to give I.4. A process for the preparation of the compound of formula I defined inclaim 1, which comprises reacting a benzyl compound of formula II

wherein L¹ represents a nucleophilically exchangeable leaving group,with a carbonylhydroxyimine of formula VII

to give a compound of formula VIII

and subsequently reacting VIII either a) first with hydroxylamine or asalt thereof and then with a compound of formula VI R²—L²  (VI)  whereinL² is a nucleophilically exchangeable leaving group, or b) with ahydroxylamine or a hydroxylammonium salt of formula IXa or IXbR²—ONH₂  IXb R²—ONH₃⊕Q⊖  IXb  where Q⊖ is the anion of an acid.
 5. Acomposition for controlling animal pests or harmful fungi, comprisingcustomary additives and an effective amount of the compound of formula Idefined in claim
 1. 6. The composition defined in claim 5, wherein theanimal pests are from the classes of insects, arachnids and nematodes.7. A method of controlling animal pests or harmful fungi, whichcomprises treating the pests or the harmful fungi, their environment orplants, areas, materials or spaces to be kept free from them with aneffective amount of the compound of formula I defined in claim
 1. 8. Acompound of formula III

wherein R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy; n is 1 to 5, and the radicals R¹ are identical ordifferent when n is other than 1; and R² is C₁-C₄-alkyl, C₃-C₆-alkenylor C₃-C₆-alkynyl, and these groups are unsubstituted, partiallyhalogenated or fully halogenated.
 9. A compound of formula IV

wherein R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy; and n is 1 to 5, and the radicals R¹ are identical ordifferent when n is other than
 1. 10. A compound of formula VII

wherein R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy; and n is 1 to 5, and the radicals R¹ are identical ordifferent when n is other than
 1. 11. A compound of formula VIIa

wherein R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy; and n is 1 to 5, and the radicals R¹ are identical ordifferent when n is other than
 1. 12. A compound of formula VIII

wherein R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy; n is 1 to 5, and the radicals R¹ are identical ordifferent when n is other than 1; and Q is C(═CHOCH₃)—COOCH₃,C(═CHCH₃)—COOCH₃, C(═NOCH₃)—COOCH₃ or C(═NOCH₃)—CONHCH₃.
 13. A compoundof formula X

wherein R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy; n is 1 to 5, and the radicals R¹ are identical ordifferent when n is other than 1; and R² is C₁-C₄-alkyl, C₃-C₆-alkenylor C₃-C₆-alkynyl, and these groups are unsubstituted, partiallyhalogenated or fully halogenated.
 14. A compound of formula XI

wherein R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy; and n is 1 to 5, and the radicals R¹ are identical ordifferent when n is other than
 1. 15. A compound of formula XIII

wherein R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy; n is 1 to 5, and the radicals R¹ are identical ordifferent when n is other than 1; and R² is C₁-C₄-alkyl, C₃-C₆-alkenylor C₃-C₆-alkynyl, and these groups are unsubstituted, partiallyhalogenated or fully halogenated.
 16. A compound of formula XV

wherein R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy; n is 1 to 5, and the radicals R¹ are identical ordifferent when n is other than 1; and R² is C₁-C₄-alkyl, C₃-C₆-alkenylor C₃-C₆-alkynyl, and these groups are unsubstituted, partiallyhalogenated or fully halogenated.
 17. A compound of formula XVI

wherein R¹ is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy orC₁-C₄-haloalkoxy; n is 1 to 5, and the radicals R¹ are identical ordifferent when n is other than 1; and R² is C₁-C₄-alkyl, C₃-C₆-alkenylor C₃-C₆-alkynyl, and these groups are unsubstituted, partiallyhalogenated or fully halogenated.